Organotin compounds are well known in the art and their application as biocides has likewise been well known for a long time in the art. The biocidal properties of a wide variety of organotin compounds, especially the tetra-substituted organotins, make them useful for the control of arachnid pests such as mites and ticks, fungi such as apple scab and woodrot organisms, weeds such as pigweed, and insects such as southern army worms, houseflies and Mexican bean beetles.
British Pat. No. 966,813 to Ziegler discloses a method for obtaining tetrasubstituted organotin compounds useful as high polymers, but no suggestion is made in this patent that these compounds might find utility in controlling insects and other pests.
U.S. Pat. No. 3,642,845 to Ramsden discloses bistrialkyltin compounds of the formula (R).sub.3 SnR'Sn(R).sub.3 wherein R is an alkyl group and R' is a hydrocarbon diradical having a minimum of 8 carbon atoms. These compounds exhibit systemic pesticidal activity, particularly against lepidoptera insect larvae, such as the Southern army worm.
U.S. Pat. No. 3,206,489 to Stamm et al. discloses tetrasubstituted tin compounds of the general formula ##EQU1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 can be alkyl radicals having from 1 to 12 carbon atoms and an aromatic hydrocarbon radical provided one of the R substituents is an alkyl radical terminating in a lower aliphatic thioacid group which is characterized by the presence of a thiocarboxyl function. These compounds are indicated as being useful as herbicides.
U.S. Pat. No. 3,591,614 to Bublitz discloses compounds of the formula ##SPC2##
Wherein R is 2-cyanoethyl, 2-carboxyethyl, or 2-carb(lower)-alkoxyethyl group. These substituted ethyl derivatives of tricyclohexyltin as indicated as being useful as acaricides for the control of mites and ticks.
An additional U.S. Pat. No. 3,641,037 to Bublitz discloses compounds of the formula ##SPC3##
wherein R is 2-furyl, 2-pyridyl, 3-pyridyl, 1-indenyl, or 2-(2-pyridyl)ethyl, these compounds being useful as pesticides, particularly for the control of mites and ticks.
German patent 2,231,814 to Peterson discloses compounds of the formula EQU (R).sub.3 SnCH.sub.2 -X
wherein X is alkyl- or arylsulfonyl, alkyl- or arylthio or dialkylamino and R is alkyl of from 1 to 14 carbon atoms. These compounds are disclosed as being useful in protective coatings against bacteria, fungi, termites and barnacles.
Peterson, in U.S. Pat. No. 3,725,446, claims some of the same compounds, R-S-CH.sub.2 -Sn-R'.sub.3, where R is alkyl of from 1 to 14 carbon atoms, aryl or substituted aryl, and R' is alkyl of 1 to 14 carbon atoms. These compounds are said to have pre-emergent and post-emergent herbicidal activity.
Peterson, in U.S. Pat. No. 3,784,580, discloses, inter alia, phenylsulfonylmethyltrihydrocarbyl stannane ((phenylsulfonylmethyl)trihydrocarbyltin) compounds of the formula (R).sub.3 SnCH.sub.2 SO.sub.2 Ph, the said compounds being useful as insecticides, acaricides, bacteriostats, fungicides and herbicides. These Peterson compounds differ from the compounds of this invention in two important respects, namely, (1) the phenylsulfonyl moiety is linked to the tin atom by a single methylene diradical instead of by a diradical having at least two carbon atoms, and (2) the phenyl group lacks the hydrocarbyl substituents.
Peterson, in U.S. Pat. No. 3,794,670, discloses a process for the preparation of alkylphenylsulfonylmethyltrihydrocarbyl stannane ((alkylphenylsulfonylmethyl)trihydrocarbyltin) compounds of the formula R.sub.3 SnCH.sub.2 SO.sub.2 R.sub.1, the said compounds being useful as pesticides and seed protecting agents. These Peterson compounds differ from the compounds of this invention in that the phenylsulfonyl moiety is linked to the tin atom by a single methylene diradical instead of by a diradical having at least two carbon atoms.
Peterson has authored a paper, "Preparation and Reactions of some Sulfur-Substituted Tetraorganotin Compounds", J. Organometal Chem. 26, 215-223 (1971). The following paragraph appears at page 218:
"[(Phenylsulfonyl)methyl]tributyltin [(IV)] was found to be unreactive toward carbon dioxide and oxygen at room temperature, while exposure of a thin layer of (IV) to air resulted in ca. 50% decomposition to phenyl methyl sulfone and tributyltin oxide within four days. These findings, when regarded in conjunction, are in accord with hydrolysis being responsible for the air sensitivity of (IV)." PA1 K. hayashi, J. Iyoda and I. Shiihara, J. Organometal. Chem., 10, 81 (1967). PA1 H. g. kuivila, Advan. Organometal Chem., 1, 47 (1964). PA1 W. p. neumann, Angew. Chem., Internat. Edit., 2, 165 (1963).
Koopmans, in U.S. Pat. No. 3,031,483, discloses compounds of the structure ##EQU2## in which R.sub.1, R.sub.2 and R.sub.3 may be the same or different and represent alkyl groups with 1-12 carbon atoms, phenyl groups or halophenyl groups, and Q represents one of a number of groups, including ##EQU3## These compounds have fungicidal and bactericidal properties.
Ayrey et al. have published a paper, J. Organometal. Chem. 35, 105-109 (1972), in which they deal with the preparation of 3-(trialkylstannyl)propyl aryl sulfides, R.sub.3 SnCH.sub.2 CH.sub.2 CH.sub.2 SR'. No utility is stated for these compounds.